Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/14—Unsaturated ethers
  • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2648—Alkali metals or compounds thereof

Definitions

• the present invention relates to novel polyethers that are homopolymers of a glycidyl ether or copolymers of a glycidyl ether and an alkylene oxide having 2 to 6 carbon atoms that have an aliphatically unsaturated bond in a terminal group or linking group and particularly that have a terminal double bond.
• the present invention further relates to methods of producing these novel polyethers.
• Polyethers having an aliphatic double bond in molecular chain terminal position are compounds useful, inter alia, as reactive surfactants for emulsion polymerization, as intermediates for such reactive surfactants, and as intermediates for polysiloxane/polyether copolymers.
• Japanese Patent No. 2,672,385 JP 2,672,385 B discloses a method of producing a polyether having the allyloxy group at one terminal by the addition polymerization of butylene oxide and ethylene oxide on allyl alcohol in the presence of a base catalyst.
• JP 2001-342156 discloses a method of producing an unsaturated aliphatic alcohol/alkylene oxide adduct by the addition polymerization of an alkylene oxide on an unsaturated aliphatic alcohol in the presence of the strong acid salt of a metal.
• JP 2002-179788 A discloses a method of producing a polyether that has an alkenyl at one terminal and hydroxyl at the other terminal; this method proceeds by the addition polymerization of an alkylene oxide on an unsaturated aliphatic alcohol in the presence of a Lewis acid catalyst or composite metal oxide catalyst.
• the structural unit of these polyethers is limited to the alkyleneoxy group.
• JP S62-059236 A discloses a method of producing a polyether having an aliphatic double bond at one molecular chain terminal and hydroxyl group at the other terminal; this method proceeds through the ring-opening polymerization of an alkylene oxide or a glycidyl ether or both in the presence of an aliphatic double bond-containing alcohol and a cationic initiator (for example, a Friedel-Crafts catalyst, protonic acid).
• JP S62-059236 A also discloses the polyether produced by this method, i.e., polyether having an aliphatic double bond at one molecular chain terminal and hydroxyl group at the other terminal.
• the molecular weight distribution has a broad polydispersity of at least 1.3 to a maximum of 7.5, and only a low-purity polyether is obtained.
• Low-purity alkenyl-monoterminated polyether with such a broad molecular weight distribution is unsuitable as a reactive surfactant for emulsion polymerization and is also unsuitable as an intermediate in the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction. It is also unsuitable as an intermediate in the production of block copolymers.
• a polyether having alkenyl at only one terminal is unsuitable as an intermediate for the production of block copolymers.
• the oxidation resistance is unsatisfactory when the alkyleneoxy group is the main structural unit.
• a problem to be addressed by the present invention is the introduction of a novel polyether that is either a straight-chain homopolymer obtained by the ring-opening addition polymerization of a glycidyl ether on a monohydric alcohol or a straight-chain copolymer obtained by the ring-opening addition copolymerization of a glycidyl ether and an alkylene oxide having 2 to5 carbon atoms on a monohydric alcohol, that has an aliphatically unsaturated bond in a molecular chain terminal group and in particular that has a terminal double bond, and that has a narrow molecular weight distribution (polydispersity).
• Another problem to be addressed by the present invention is the introduction of a polyether that exhibits an excellent oxidation resistance in addition to being equipped with the aforementioned characteristic features.
• Another problem to be addressed by the present invention is the introduction of a novel polyether that is either a straight-chain or branched homopolymer obtained by the ring-opening addition polymerization of a glycidyl ether on a dihydric to hexahydric alcohol or a straight-chain or branched copolymer obtained by the ring-opening addition polymerization of a glycidyl ether and an alkylene oxide having 2 to 6 carbon atoms on a dihydric to hexahydric alcohol, that has an aliphatically unsaturated bond in a molecular chain terminal group or in a linking group and in particular that has a terminal double bond, and that has a narrow molecular weight distribution (polydispersity).
• Another problem to be addressed by the present invention is the introduction of a polyether that exhibits an excellent oxidation resistance in addition to being equipped with the aforementioned characteristic features.
• a further problem to be addressed by the present invention is the introduction of methods that can produce precisely the aforementioned polyethers in good purities.
• the polyethers of claim 1 and particularly claims 2 to 5 as well as their dependent claims are novel polyethers that are straight-chain homopolymers obtained by the ring-opening addition polymerization of a glycidyl ether on a monohydric alcohol or straight-chain copolymers obtained by the ring-opening addition copolymerization of a glycidyl ether and an alkylene oxide on a monohydric alcohol; that have an aliphatically unsaturated bond in a molecular chain terminal group and in particular that have a terminal double bond; and that have a small molecular weight distribution (polydispersity) of 1.25 to 1.00,.
• polyether has the small molecular weight distribution (polydispersity) of 1.25 to 1.00, a particular reaction product or polymer can be very efficiently obtained when the polyether is subjected to a hydrosilylation reaction or radical polymerization.
• the hydrosilylation reaction product or radical polymerization product may contain a substituted alkyleneoxy group or a substituted alkyleneoxy group and an alkyleneoxy group.
• the polyether according to claim 9 and particularly according to claim 10 exhibits an excellent oxidation resistance while also having the characteristic features cited above.
• the polyethers of claim 11 and particularly claims 12 and 16 as well as their dependent claims are novel polyethers that are straight-chain or branched homopolymers obtained by the ring-opening addition polymerization of a glycidyl ether on a divalent to hexavalent alcohol or straight-chain or branched copolymers obtained by the ring-opening addition polymerization of a glycidyl ether and an alkylene oxide having 2 to 6 carbon atoms on a divalent to hexavalent alcohol; that have an aliphatically unsaturated bond in a molecular chain terminal group or in a linking group and in particular that have a terminal double bond; and that have a small molecular weight distribution (polydispersity) of 1.25 to 1.00.
• polyether has the small molecular weight distribution (polydispersity) of 1.25 to 1.00, a particular reaction product or polymer can be very efficiently obtained when the polyether is subjected to a hydrosilylation reaction or radical polymerization.
• the hydrosilylation reaction product or radical polymerization product may contain a substituted alkyleneoxy group or a substituted alkyleneoxy group and an alkyleneoxy group.
• the polyethers according to claim 20 and particularly according to claim 21 exhibit an excellent oxidation resistance while also having the characteristic features cited above. Methods of producing a polyether according to claims 22 to 28 and their dependent claims can produce precisely the above-cited polyethers at good purities.
• the polyether of claim 1 is characteristically represented by general formula (1) R-O-X n -Z m -Y (1) ⁇ in the formula, R is a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or is a group comprising said monovalent hydrocarbyl group having an ether linkage (CO-C) therein; n is 1 to 200; m is 0 to 200; 0 ⁇ n /( n + m ) ⁇ 1; Z is an alkyleneoxy group having 2 to 6 carbon atoms; Y is hydrogen atom or is a group selected from the group consisting of a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, an acyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, and glycidyl group; and X is a group represented by general formula
• This polyether is a polyglycidyl ether having a main chain comprising only the X groups given by general formulas (2) and (3) or is a glycidyl ether/alkylene oxide copolymer having a main chain comprising both the X groups given by general formulas (2) and (3) and Z groups (alkyleneoxy groups having 2 to 6 carbon atoms).
• a group R (a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein) is bonded at one terminal and a group Y (hydrogen atom or a group selected from the group consisting of a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, an acyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, and glycidyl group) is bonded at the other terminal and either R or Y contains an aliphatically unsaturated bond or both R and Y contain an aliphatically unsaturated bond.
• R a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or a group comprising said mono
• the group X is a divalent organic group derived from a glycidyl ether with general formula (6) (R 1 in the formula is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group). That is, the group X is a structural unit produced by the ring-opening polymerization of the glycidyl ether with general formula (6).
• the number n of X groups in a single molecule of the polyether, that is, the average degree of polymerization, is 1 to 200.
• This average degree of polymerization is preferably 2 to 70 and more preferably is 3 to 55, viewed from the perspective of obtaining an excellent balance among such properties as the capacity to lower the surface tension, permeation capacity, cleansing performance, emulsification capacity, solubilization capacity, and compatibility with various organic solvents and water.
• the group Z is an alkyleneoxy group having 2 to 6 carbon atoms and is a divalent organic group derived from an alkylene oxide.
• the group Z is a structural unit produced by the ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms.
• the number m of Z groups in a single molecule of the polyether that is, the average degree of polymerization, is 0 to 200. This average degree of polymerization is preferably 0 to 50 viewed from the perspective of obtaining an excellent balance among such properties as the capacity to lower the surface tension, permeation capacity, cleansing performance, emulsification capacity, solubilization capacity, and compatibility.
• n /( n + m ) designates the proportion of X groups in the polyether main chain and is greater than 0 but less than or equal to 1. As this value approaches 1, the proportion for the alkyleneoxy group declines and the oxidation resistance improves.
• the configuration of the X and Z groups may be random, alternating, block, or a combination of the preceding.
• the RO group may also be bonded to a group Z.
• the Y group may also be bonded to a group X.
• the X and Z groups assume a random configuration in the case of a simple ring-opening copolymerization between the glycidyl ether with general formula (6) and an alkylene oxide having 2 to 6 carbon atoms.
• the product of the polymerization is a block copolymer when ring-opening polymerization is first carried out with the glycidyl ether with general formula (6) followed by ring-opening polymerization with an alkylene oxide having 2 to 6 carbon atoms, or when ring-opening polymerization is first carried out with the alkylene oxide having 2 to 6 carbon atoms followed by ring-opening polymerization with the glycidyl ether with general formula (6).
• the configuration for the X and Z groups is preferably random followed by block and then a mixture of block and random.
• the alkyleneoxy group can be exemplified by ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, and cyclohexeneoxy. Viewed from the perspective of the capacity to impart hydrophilicity, the ethyleneoxy group is preferred, followed by the propyleneoxy group. A single molecule may also contain a mixture of ethyleneoxy and propyleneoxy groups.
• Either R or Y or both R and Y must contain an aliphatically unsaturated bond in each molecule of the polyether with general formula (1), and this aliphatically unsaturated bond is preferably a terminal double bond based on a consideration of the radical polymerizability and hydrosilylation reactivity.
• Preferred embodiments are the polyether according to claim 2, which is characterized by R being a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein and Y being hydrogen atom; the polyether according to claim 3, which is characterized by R being a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein and Y being a group selected from the group consisting of an aliphatically unsaturated bond-free monovalent hydrocarbyl group that contains no more than 20 carbon atoms, an aliphatically unsaturated bond-free acyl group that contains no more than 20 carbon atoms, and glycidyl group; the polyether according to claim 4, which is characterized by R being an aliphatically unsaturated bond-free monovalent hydrocarby
• R 1 in the group X in the polyether with general formula (1) and the four polyethers described above is preferably an aliphatically unsaturated bond-free monovalent hydrocarbyl group in order to enable the utilization in an ensuing reaction of only the terminal double bond in R, or only the terminal double bond in Y, or only the terminal double bonds in R and Y.
• 0.5 ⁇ n /( n + m ) ⁇ 1 is preferred and 0.9 ⁇ n /( n + m ) ⁇ 1 is more preferred.
• R in general formula (1) is a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or is a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein.
• Representative examples of R in its embodiment as a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond are a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms and an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms .
• the number of ether linkages in a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein is preferably one to three and more preferably is one.
• Y is hydrogen atom or is a group selected from the group consisting of monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, an acyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond, and glycidyl group.
• Representative examples of Y in its embodiment as a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond are a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms and an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms.
• Y in its embodiment as an acyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond are a double bond-terminated acyl group having 2 to 20 carbon atoms and aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms .
• the double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms constituting R or Y can be exemplified by alkenyl, alkenylphenyl, and alkenylaralkyl.
• the group comprising this monovalent hydrocarbyl group having an ether linkage (C-O-C) therein can be exemplified by alkenyloxyalkyl and alkenyloxyphenyl.
• the aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms constituting R or Y can be exemplified by alkyl, phenyl, alkylphenyl, aralkyl, and alkylaralkyl.
• the group comprising this monovalent hydrocarbyl group having an ether linkage (C-O-C) therein can be exemplified by alkyloxyalkyl and alkyloxyphenyl.
• the alkenyl encompassed by R and Y as cited above can be exemplified by vinyl, allyl, methallyl, 3-butenyl, 1,1-dimethyl-2-propenyl, i.e., the group represented by the formula 4-pentenyl, 5-hexenyl, 10-undecenyl, and isoprenyl.
• the alkenylphenyl encompassed by R and Y as cited above can be exemplified vinylphenyl and allylphenyl.
• the alkenylaralkyl encompassed by R and Y as cited above can be exemplified by vinylbenzyl and allylbenzyl.
• the alkenyloxyalkyl encompassed by R and Y as cited above can be exemplified by vinyloxyethyl, allyloxyethyl, butenoxyethyl, pentenyloxyethyl, hexenyloxyethyl, allyloxypropyl.
• the alkenyloxyphenyl encompassed by R and Y as cited above can be exemplified by vinyloxyphenyl and allyloxyphenyl.
• the alkyl encompassed by R and Y as cited above can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, and an alkyl having 7 to 20 carbon atoms.
• the alkylphenyl encompassed by R and Y as cited above can be exemplified by tolyl, xylyl, ethylphenyl, propylphenyl, and octylphenyl.
• the alkylaralkyl encompassed by R and Y as cited above can be exemplified by tolylmethyl.
• alkyloxyalkyl i.e., alkoxyalkyl encompassed by R as cited above can be exemplified by methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, and propoxypropyl.
• alkyloxyphenyl i.e., alkoxyphenyl encompassed by R as cited above can be exemplified by methoxyphenyl, ethoxyphenyl, and propoxyphenyl.
• the group having 2 to 20 carbon atoms constituting Y can be exemplified by acryl, methacryl, crotonyl, and undecenoyl.
• the aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms constituting Y can be exemplified by acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl tetradecanoyl, hexadecanoyl, octadecanoyl, and palmitoyl.
• the R 1 in the group X in general formulas (2) and (3) is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group.
• R 1 in the group X is preferably an aliphatically unsaturated bond-free monovalent hydrocarbyl group in order to enable the utilization in an ensuing reaction of only the terminal double bond in R, or only the terminal double bond in Y, or only the terminal double bonds in R and Y.
• the aliphatically unsaturated bond-free monovalent hydrocarbyl group can be exemplified by alkyl, phenyl, alkylphenyl, and aralkyl.
• the monovalent fluorohydrocarbyl group also preferably lacks an aliphatically unsaturated bond and can be exemplified by perfluoroalkyl.
• the alkyl can be exemplified by methyl, ethyl, propyl, butyl, pentyl, and hexyl; the alkylphenyl can be exemplified by tolyl and xylyl; and the aralkyl can be exemplified by benzyl.
• the perfluoroalkyl can be exemplified by trifluoromethyl, pentafluoroethyl, trifluoropropyl, and pentafluorobutyl.
• -X n - is typically a homopolymer but may be a copolymer. That is, it may be a copolymer comprising a plurality of groups X that have different groups R 1 (for example, alkyl and phenyl or methyl and butyl).
• the copolymer is ordinarily a random copolymer, but may be a block copolymer.
• R 1 preferably has a small number of carbon atoms in order to impart surface activity to the polyether of claim 1 and the polyethers cited in the preceding embodiments, and an alkyl group having 1 to 4 carbon atoms, and particularly an alkyl group having one carbon atom (i.e., methyl), is preferred.
• R 1 is preferably a mixture of alkyl groups having different numbers of carbon atoms (for example, methyl and butyl).
• the polyether with general formula (1) according to claim 1 has a molecular weight distribution (polydispersity) determined versus a polystyrene standard of 1.25 to 1, and preferably 1.10 to 1.00.
• the molecular weight distribution (polydispersity) determined versus a polystyrene standard can be determined by the method described in Examples. Polyether having this small molecular weight distribution (polydispercity) can be readily produced by the preparative methods described below.
• the group R in the polyether according to claim 2 is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or is a group comprising this a monovalent hydrocarbyl group having an ether linkage (C-O-C) therein, and this terminal double bond is highly reactive.
• This polyether because it has a hydrophobic group R at one terminal and because the Y at the other terminal is hydrogen atom, thus bears hydroxyl group at the other terminal and therefore exhibits an excellent surface activity.
• R is double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms
• R 1 is an alkyl group having 1 to 4 carbon atoms and particularly methyl
• the group Z is either not present or, if present, is ethyleneoxy, propyleneoxy or ethyleneoxy + propyleneoxy.
• the polyether according to claim 2 is useful as a nonionic surfactant, as a reactive surfactant for emulsion polymerization, and as an intermediate in the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• An anionic reactive surfactant can be synthesized by modification of the hydroxyl group at the other terminal.
• the ammonium salt of a sulfate ester can be synthesized by reaction with sulfamic acid.
• modification reactions such as sulfonation, phosphate esterification, carboxymethylation, and so forth, can be carried out according to the methods described on page 7 of JP H03-503168 A .
• the reactive surfactant produced in this manner can be used as an emulsifying agent for emulsion polymerization, as a modifier for polymers, and as an intermediate in the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• R has a terminal double bond, which is highly reactive, and the Y at the other terminal does not have an aliphatically unsaturated bond.
• This polyether is therefore useful as a starting material for copolymerization with another vinyl monomer and as an intermediate for the preparation of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• the Y in this polyether is glycidyl group, the high reactivity makes this polyether useful as a modifier for polymers and resins.
• the group R does not contain an aliphatically unsaturated bond and the Y at the other terminal has a terminal double bond. Due to the high reactivity of this terminal double bond, this polyether is useful as a starting material for copolymerization with another vinyl monomer, as a starting material for the preparation of polyether-modified organopolysiloxanes using the hydrosilylation reaction, and as a base component of crosslinkable compositions.
• the group R has a terminal double bond and the group Y also has a terminal double bond, making this polyether useful as a starting material for the preparation of block copolymers and as a base component of crosslinkable compositions.
• polyethers represented by general formula (1) the polyether according to claim 2 - in which R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein and Y is hydrogen atom - can be readily produced by
• polyethers represented by general formula (1) the polyether according to claim 6 - in which R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or is a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein, R 1 in the group X is an aliphatically unsaturated bond-free monovalent hydrocarbyl group, and Y is hydrogen atom - can be readily produced by
• the monohydric alcohol represented by general formula (5): ROH (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein) is the source of the group R in general formula (1).
• the glycidyl ether with general formula (6) is ring-opening addition polymerized by itself on the hydroxyl group of this monohydric alcohol, or the glycidyl ether with general formula (6) and an alkylene oxide having 2 to 6 carbon atoms are ring-opening addition copolymerized on this hydroxyl group.
• ROH (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein)
• ROH can be exemplified by allyl alcohol, methallyl alcohol, 3-butenyl alcohol, 4-pentenyl alcohol, 5-hexenyl alcohol, 10-undecenyl alcohol, isoprenyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, eugenol, and o-allylphenol.
• the alkenyl group having 3 to 20 carbon atoms in these alcohols may be branched, while the alkenyl group having 5 to 20 carbon atoms may be cyclic.
• the glycidyl ether given by general formula (6) is the source of the group X in general formula (1) and is converted into the group X by the ring-opening polymerization.
• This glycidyl ether can be exemplified by alkyl glycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, and butyl glycidyl ether; phenyl glycidyl ether; and perfluoroalkyl glycidyl ethers such as trifluoromethyl glycidyl ether and trifluoropropyl glycidyl ether.
• a single glycidyl ether or a mixture of two or more glycidyl ethers may be subjected to the polymerization. Because glycidyl ethers are typically produced by the reaction of epichlorohydrin and an alcohol, they frequently contain unreacted epichlorohydrin and organochlorine compound by-products. Removing the organochlorine compounds by treating the glycidyl ether with a basic alkali metal compound and thereafter purifying by distilling the epoxy compound makes it possible to obtain high-purity polyether with a narrow molecular weight distribution and to reduce the amount of the base catalyst used in the polymerization, and this procedure is therefore preferred.
• the alkylene oxide having 2 to 6 carbon atoms is the source of the group Z in general formula (1) and is converted into the group Z by the ring-opening polymerization.
• the alkylene oxide having 2 to 6 carbon atoms can be exemplified by ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and hexylene oxide.
• a single alkylene oxide having 2 to 6 carbon atoms or a mixture of two or more alkylene oxides having 2 to 6 carbon atoms may be subjected to the polymerization.
• the glycidyl ether with general formula (6) and the alkylene oxide having 2 to 6 carbon atoms may be submitted to the copolymerization reaction at the molar ratio required in view of the number n and the number m in general formula (1).
• the ring-opening polymerization of the glycidyl ether with general formula (6) is carried out using a base catalyst (also known as a basic catalyst).
• the ring-opening copolymerization of the glycidyl ether with general formula (6) with the alkylene oxide having 2 to 6 carbon atoms is carried out using a base catalyst (also known as a basic catalyst).
• a base catalyst also known as a basic catalyst
• polymerization goes forward as a living polymerization and provides a polyether ether that contains little reaction by-product and has a small molecular weight distribution (polydispersity) such as 1.25 to 1.00.
• Usable base catalysts can be exemplified by alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and so forth; alkali metal alcoholates such as potassium methoxide, potassium ethoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, and so forth; and various amine compounds, most prominently triethylamine.
• alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and so forth
• alkali metal alcoholates such as potassium methoxide, potassium ethoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, and so forth
• various amine compounds most prominently triethylamine.
• a suitable amount of catalyst is 0.005 to 2.0 weight% (as solids) with reference to the total amount of the reaction starting materials (total amount charged) and is more preferably 0.03 to 1.0 weight% (as solids).
• a polyether by-product is produced that is blocked with carbinol groups at both molecular terminals
• a polyether by-product is produced that is blocked with an alkoxy group at one terminal and by an carbinol group at the other molecular terminal.
• the ROH (initiator) is partially alkali-metalated by carrying out a complete reaction between the ROH and alkali metal hydroxide or alkali metal alcoholate, and this is followed by removal of the water or alcohol by-product by a suitable method, for example, distillation by heating under reduced pressure.
• a suitable method for example, distillation by heating under reduced pressure.
• a polyether blocked with t-butoxy at one molecular terminal is essentially not produced in a secondary reaction and the ring-opening polymerization proceeds via partially alkali metalated ROH produced by an exchange reaction with the ROH.
• potassium t-butoxide is preferred for the polymerization catalyst because it enables the production of a high-purity polyether without employing the aforementioned procedure for removing the alcohol or water by-product.
• the polymerization is preferably carried out in a solvent that is inert with respect to the base catalyst-mediated ring-opening polymerization, such as a hydrocarbon solvent such as toluene, xylene, and so forth, or an ether solvent such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and so forth.
• a solvent that is inert with respect to the base catalyst-mediated ring-opening polymerization such as a hydrocarbon solvent such as toluene, xylene, and so forth, or an ether solvent such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and so forth.
• the glycidyl ether with general formula (6) is preferably gradually added dropwise, or the glycidyl ether with general formula (6) and the alkylene oxide are each preferably gradually added dropwise in sequence (no particular sequence is specified), or a mixture of the glycidyl ether with general formula (6) and the alkylene oxide is preferably added dropwise.
• the preferred polymerization reaction temperature is 50 to 200°C.
• the status of the consumption of the starting glycidyl ether with general formula (6) and the starting alkylene oxide having 2 to 6 carbon atoms is monitored, for example, by gas chromatography (GLC), gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), and so forth, while carrying out the ring-opening polymerization at the aforementioned temperature.
• a random copolymer may be obtained as follows: by the ring-opening copolymerization of a mixture of one glycidyl ether and one alkylene oxide; by the ring-opening copolymerization of two or more glycidyl ethers and one alkylene oxide; by the ring-opening copolymerization of a mixture of one glycidyl ether and two or more alkylene oxides; or by the ring-opening copolymerization of a mixture of two or more glycidyl ethers and two or more alkylene oxides.
• a block copolymer is obtained by running the ring-opening polymerization of the glycidyl ether with general formula (6) and, once its consumption has been confirmed, adding the alkylene oxide having 2 to 6 carbon atoms and running its ring-opening polymerization.
• a block copolymer may also be obtained by running a ring-opening polymerization on the alkylene oxide having 2 to 6 carbon atoms and, once its consumption has been confirmed, adding the glycidyl ether with general formula (6) and running its ring-opening polymerization.
• -X n - is elaborated as a random copolymer by running ring-opening copolymerization on a mixture of a plurality of glycidyl ethers that have different groups R 1 (for example, alkyl and phenyl, methyl and butyl).
• -Z m - is elaborated as a random copolymer by running ring-opening copolymerization on a mixture of different alkylene oxides.
• -X n - is obtained as a block copolymer by running a ring-opening polymerization with the glycidyl ether with general formula (6), and, once its consumption has been confirmed, adding a glycidyl ether with general formula (6) that has a different R 1 and running the ring-opening polymerization.
• -Z m - is obtained as a block copolymer by running a ring-opening polymerization with a first alkylene oxide, and, once its consumption has been confirmed, adding a second, different alkylene oxide and running the ring-opening polymerization.
• a polyether with general formula (1) (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (CO-C) therein, n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m ) ⁇ 1, Z is an alkyleneoxy group having 2 to 20 carbon atoms, X is a divalent group represented by the aforementioned general formula (2) or (3) (wherein R 1 is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group), and Y is hydrogen atom) can be produced by these polymerization reactions when the reaction is stopped by the addition - after confirmation of the consumption of the glycidyl ether with general formula (6) or the glycidyl ether with general formula (6) and the alkylene oxide having 2 to 6 carbon atoms - of organic acid or inorganic acid in the amount necessary to neutral
• the method of producing a polyether according to claim 23 is described in the following.
• the polyether with general formula (1) as specified in claim 3 (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein,
• X is a group represented by the aforementioned general formula (2) or (3) (wherein R 1 is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group), n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m ) ⁇ 1, Z is an alkyleneoxy group having 2 to 6 carbon atoms, and
• Y is a group selected from the group consisting of an aliphatically unsaturated bond-free monovalent hydrocarbyl group that contains no more than 20 carbon atoms, an aliphatically unsaturated bond-free acyl group that contains no
• the polyether under consideration can be readily produced by carrying out a ring-opening polymerization or a ring-opening copolymerization, in the presence of a base catalyst and amonohydric alcohol with general formula (5) ROH (5) (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein), of only the glycidyl ether represented by general formula (6) or of this glycidyl ether and an alkylene oxide having 2 to 6 carbon atoms (R 1 in the formula is a monovalent hydrocarbyl group or a monovalent fluorohydrocarbyl group); confirming that the glycidyl ether with general formula (6), or the glycidyl ether with general formula (6) and the an alkylene oxide having 2 to 6 carbon atoms, has been consumed and after this confirmation replacing the Y with
• the aliphatically unsaturated bond-free hydrocarbyl monohalide having no more than 20 carbon atoms can be exemplified by alkyl chlorides having no more than 20 carbon atoms and alkyl bromides having no more than 20 carbon atoms. Specific examples are propyl chloride, butyl chloride, hexyl chloride, octyl chloride, decyl chloride, phenyl chloride, propyl bromide, butyl bromide, hexyl bromide, octyl bromide, decyl bromide, and phenyl bromide.
• the aliphatically unsaturated bond-free acyl monohalide having no more than 20 carbon atoms can be exemplified by saturated aliphatic acid chlorides having no more than 20 carbon atoms and saturated aliphatic acid bromides having no more than 20 carbon atoms. Specific examples are acetyl chloride, propionyl chloride, benzoyl chloride, acetyl bromide, propionyl bromide, and benzoyl bromide.
• the method of producing a polyether according to claim 25 is described in the following.
• the polyether with general formula (1) as specified in claim 5 (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or is a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein, n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m ) ⁇ 1,
• X is a group represented by the aforementioned general formula (2) or (3), Z is an alkyleneoxy group having 2 to 6 carbon atoms, and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or an aliphatically unsaturated bond-containing acyl group having 2 to 20 carbon atoms
• R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or an aliphatically unsaturated bond-containing
• the polyether under consideration can be readily produced by carrying out a ring-opening polymerization or a ring-opening copolymerization, in the presence of a base catalyst and a monohydric alcohol with general formula (5) ROH (5) (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein), of only the glycidyl ether represented by general formula (6) or of this glycidyl ether and an alkylene oxide having 2 to 6 carbon atoms (R 1 in the formula is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group); confirming that the glycidyl ether with general formula (6), or the glycidyl ether with general formula (6) and the alkylene oxide having 2 to 6 carbon atoms, has been consumed and after this confirmation replacing the Y with an alkal
• the polyether with general formula (1) as specified in claim 4 (in the formula, R is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein, n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m ) ⁇ 1, X is a group represented by the aforementioned general formula (2) or (3) (in the formula, R 1 is a monovalent hydrocarbyl group or monovalent fluorohydrocarbyl group), Z is an alkyleneoxy group having 2 to 6 carbon atoms, and Y is an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms or an aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms) can be readily produced by
• the polyether according to claim 24 is described in the following.
• ROH (in the formula, R is an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein)
• ROH can be exemplified by methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, alkyl alcohols having 7 to 20 carbon atoms, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.
• the alkyl having 3 to 30 carbon atoms in these alcohols may be branched, while the alkyl having 5 to 20 carbon atoms may be cyclic.
• the alkali metal hydroxide used in the preceding reactions can be exemplified by sodium hydroxide and potassium hydroxide.
• the double bond-terminated monovalent hydrocarbyl monohalide having 2 to 20 carbon atoms can be exemplified by an alkenyl chloride having 2 to 20 carbon atoms and an alkenyl bromide having 2 to 20 carbon atoms. Specific examples are vinyl chloride, allyl chloride, allyl bromide, and methallyl chloride.
• the double bond-terminated acyl monohalide can be exemplified by a double bond-terminated unsaturated aliphatic acid chlorides having 2 to 20 carbon atoms and a double bond-terminated unsaturated aliphatic acid bromides having 2 to 20 carbon atoms.
• Specific examples are acrylic chloride, methacrylic chloride, crotonic chloride.
• a polyether which general formula (1) (wherein R in the formula is a monovalent hydrocarbyl group having 2 to 20 carbon atoms lacking a terminal double bond or is a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein, X is a group represented by the aforementioned general formula (2) or (3), n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m ) ⁇ 1, Z is an alkyleneoxy group having 2 to 6 carbon atoms, and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms) is obtained by converting the other terminal of the molecular chain to the alkali alcoholate by charging alkali metal hydroxide at or in excess of the stoichiometric quantity with respect to the number of moles of hydroxyl in the ROH used and thereafter reacting with double
• the polyether of claim 11 is represented by general formula (4) R 2 (-O-X n -Z m -Y) p (4) ⁇ in the formula, R 2 is a p-valent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or a group comprising said p-valent hydrocarbyl group having an ether linkage (C-O-C) therein;
• X is a group with the aforementioned general formula (2) or general formula (3);
• n is 1 to 200;
• m is 0 to 200; 0 ⁇ n /( n + m ) ⁇ 1;
• Z is an alkyleneoxy group having 2 to 6 carbon atoms;
• p is an integer with a value of 2 to 6;
• Y is hydrogen atom or is a group selected from the group consisting of a monovalent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphat
• R 2 is a p-valent hydrocarbyl group that contains no more than 20 carbon atoms and that may contain an aliphatically unsaturated bond or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein (wherein p is 2 to 6).
• R 1 in the group X is preferably an aliphatically unsaturated bond-free monovalent hydrocarbyl group, and, viewed from the standpoint of the oxidation resistance, n and m preferably satisfy 0.5 ⁇ n /( n + m ) ⁇ 1 and more preferably satisfy 0.9 ⁇ n /( n + m ) ⁇ 1.
• the number of ether linkages in the group comprising the p -valent hydrocarbyl group having an ether linkage (C-O-C) therein is preferably 1 to 3 and more preferably is 1.
• the definitions, preferred embodiments, and examples of the group X, n , the group Z, m , 0 ⁇ n /( n + m ) ⁇ 1, the internal configuration of -X n -, the internal configuration of -Z n -, the configuration of -X n - and -Z n -, and the molecular weight distribution (polydispercity) are as described for the polyether according to claim 1 and its dependent claims.
• R 2 is a double bond-terminated divalent to hexavalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising this divalent to hexavalent hydrocarbyl group having an ether linkage (C-O-C) therein
• Y is hydrogen atom
• p is 2 to 6, is a preferred embodiment because it has a terminal double bond and a terminal hydroxyl group. p is 2 in a more preferred embodiment thereamong.
• R 2 is a double bond-terminated divalent to hexavalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising this divalent to hexavalent hydrocarbyl group having an ether linkage (C-O-C) therein
• Y is an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms or an aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms
• p is 2 to 6, is a preferred embodiment because it has a terminal double bond.
• p is 2 in a more preferred embodiment thereamong.
• R 2 is an aliphatically unsaturated bond-free p -valent hydrocarbyl (i.e., divalent to hexavalent hydrocarbyl) group having no more than 20 carbon atoms or a group comprising this divalent to hexavalent hydrocarbyl group having an ether linkage (C-O-C) therein
• Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms
• p is 2 to 6, is also a preferred embodiment.
• p is 2 in a more preferred embodiment thereamong.
• R 2 is examples of R 2 in its implementation as a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising this p-valent hydrocarbyl group having an ether linkage (CO-C) therein.
• R 2 in its implementation as an aliphatically unsaturated bond-free divalent hydrocarbyl group having no more than 20 carbon atoms are alkylene, phenylene, alkylenephenylene, and alkylenephenylenealkylene.
• groups comprising this divalent hydrocarbyl group having an ether linkage (C-O-C) therein are alkyleneoxyalkylene and alkyleneoxyphenylene.
• the alkylene can be exemplified by ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene.
• the alkylenephenylene can be exemplified by ethylenephenylene.
• the alkylenephenylenealkylene can be exemplified by ethylenephenyleneethylene.
• R 1 in the group X in the polyethers of claims 12 and 16 and their embodiments is preferably an aliphatically unsaturated bond-free monovalent hydrocarbyl group in order to enable the utilization in an ensuing reaction of only the terminal double bond in R 2 , or only the terminal double bond in Y, or only the terminal double bonds in R 2 and Y.
• 0.5 ⁇ n /( n + m ) ⁇ 1 is preferred and 0.9 ⁇ n /( n + m ) ⁇ 1 is more preferred.
• a polyether in which Y is hydrogen atom exhibits a high reactivity in the terminal double bond in R 2 , which is a double bond-terminated divalent or hexavalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising this divalent or hexavalent hydrocarbyl group having an ether linkage (C-O-C) therein.
• Such polyether has a hydroxyl group at the other terminal since Y is hydrogen atom and thus exhibits an excellent surface activity.
• an anionic reactive surfactant can be synthesized by modification of this hydroxyl group.
• an ammonium salt of a sulfate ester can be synthesized by reacting this hydroxyl group with sulfamic acid.
• modification reactions such as sulfonation, phosphate esterification, carboxymethylation, and so forth, can be carried out at this hydroxyl group according to the methods described on page 7 of JP H03-503168 A .
• the reactive surfactant produced in this manner is useful as a reactive emulsifying agent for emulsion polymerization, as a modifier for polymers, and as an intermediate in the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• a polyether in which Y is an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms or an aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms exhibits a high reactivity in the terminal double bond in R 2 - which is a double bond-terminated divalent or hexavalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising this divalent or hexavalent hydrocarbyl group having an ether linkage (C-O-C) therein - and lacks reactivity in Y. It is therefore useful as a monomer for copolymerization with other vinyl monomer and as an intermediate in the production of polyether-modified organopolysiloxanes via the hydrosilylation reaction.
• This polyether is therefore useful as a starting material for the production of block copolymer and as a base component in crosslinkable compositions.
• R 2 which is a linking group, does not contain an aliphatically unsaturated bond and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms.
• Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms.
• it has terminal double bonds at its molecular chain terminals and, because these terminal double bonds are highly reactive, it is useful as a monomer for copolymerization with other vinyl monomer and as an intermediate in the production of polyether-modified organopolysiloxanes via the hydrosilylation reaction.
• a polyether with general formula (4) according to claim 12 (in the formula, R 2 is double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or is a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein;
• X is a group represented by the aforementioned general formula (2) or (3);
• n is 1 to 200;
• m is 0 to 200; 0 ⁇ n /( n + m) ⁇ 1;
• Z is an alkyleneoxy group having 2 to 6 carbon atoms;
• p is an integer with a value of 2 to 6; and
• Y is hydrogen atom
• having a molecular weight distribution (polydispersity) determined versus a polystyrene standard of 1.25 to 1.00 can be readily produced by
• a polyether with general formula (4) according to claim 12 (in the formula, R 2 is a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or is a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein;
• X is a group represented by the aforementioned general formula (2) or (3);
• n is 1 to 200;
• m is 0 to 200; 0 ⁇ n /( n + m) ⁇ 1;
• Z is an alkyleneoxy group having 2 to 6 carbon atoms;
• p is an integer with a value of 2 to 6; and
• Y is a group selected from the group consisting of an aliphatically unsaturated bond-free monovalent hydrocarbyl group having no more than 20 carbon atoms, an aliphatically unsaturated bond-free acyl group having no more than 20 carbon atoms, and glycidy
• the polyether under consideration can be readily produced by confirming the consumption of the glycidyl ether with general formula (6) or the glycidyl ether with general formula (6) and the alkylene oxide having 2 to 6 carbon atoms and thereafter replacing the Y with alkali metal by reacting with an alkali metal hydroxide; then reacting with an aliphatically unsaturated bond-free hydrocarbyl monohalide having no more than 20 carbon atoms, an aliphatically unsaturated bond-free acyl monohalide having no more than 20 carbon atoms, or epichlorohydrin; and removing the alkali metal salt by-product by a method such as filtration, adsorptive removal with an adsorbent, and so forth.
• a polyether with general formula (4) according to claim 16 (in the formula, R 2 is an aliphatically unsaturated bond-free p -valent hydrocarbyl group having no more than 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein,
• X is a group represented by the aforementioned general formula (2) or (3), n is 1 to 200, m is 0 to 200, 0 ⁇ n /( n + m) ⁇ 1, Z is an alkyleneoxy group having 2 to 6 carbon atoms, p is an integer with a value of 2 to 6, and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms) and having a molecular weight distribution (polydispersity) determined versus a polysty
• the polyether under consideration can be readily produced by confirming the consumption of the glycidyl ether with general formula (6) or the glycidyl ether with general formula (6) and an alkylene oxide having 2 to 6 carbon atoms and thereafter replacing the Y with alkali metal by reacting with an alkali metal hydroxide; then reacting with a double bond-terminated hydrocarbyl monohalide having 2 to 20 carbon atoms or a double bond-terminated acyl monohalide having 2 to 20 carbon atoms; and removing the alkali metal salt by-product by a method such as filtration, adsorptive removal with an adsorbent, and so forth.
• the p -hydric alcohol represented by general formula (7): R 2 (OH) p (in the formula, R 2 is a double bond-terminated p- valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said p- valent hydrocarbyl group having an ether linkage (C-O-C) therein) is the source of the R 2 group in general formula (4).
• the glycidyl ether with general formula (6) is ring-opening addition polymerized by itself on the hydroxyl thereof.
• the glycidyl ether with general formula (6) and an alkylene oxide having 2 to 6 carbon atoms are ring-opening addition polymerized on the hydroxyl thereof.
• the p-hydric alcohol represented by general formula (7): R 2 (OH) p (in the formula, R 2 is an aliphatically unsaturated bond-free p -valent hydrocarbyl group having no more than 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein) is the source of the R 2 group in general formula (4).
• the glycidyl ether with general formula (6) is ring-opening addition polymerized by itself on the hydroxyl thereof.
• the glycidyl ether with general formula (6) and an alkylene oxide having 2 to 6 carbon atoms are ring-opening addition polymerized on the hydroxyl thereof.
• R 2 (OH) p R 2 is a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein
• R 2 (OH) p R 2 is a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein
• R 2 (OH) p R 2 is a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein
• R 2 (OH) p R 2 is a double bond-terminated p -valent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said p -valent
• the p -hydric alcohol yielded by the allyloxylation of a portion of the hydroxyl in a dihydric to hexahydric unsaturated aliphatic alcohol can be exemplified by glycerol monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, triglycerol monoallyl ether, xylitol monoallyl ether, and glucose monoallyl ether.
• R 2 (OH) p R 2 is an aliphatically unsaturated bond-free p -valent hydrocarbyl group having no more than 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein
• R 2 (OH) p R 2 is an aliphatically unsaturated bond-free p -valent hydrocarbyl group having no more than 20 carbon atoms or a group comprising said p -valent hydrocarbyl group having an ether linkage (C-O-C) therein
• dihydric to hexahydric saturated aliphatic alcohols the p -hydric alcohol yielded by alkoxylation of a portion of the hydroxyl in a trihydric to hexahydric saturated aliphatic alcohol, dihydric to tetrahydric phenol, and dihydric to tetrahydric alkylphenol.
• the dihydric to hexahydric saturated aliphatic alcohol can be exemplified by ethylene glycol, propylene glycol, butylene glycol, glycerol, pentitols such as D-arabitol, and hexitols such as D-sorbitol and D-mannitol.
• the other starting materials, the polymerization conditions, the reaction conditions, and so forth in the method of producing a polyether according to claims 26, 27, and 28 are the same as already described in the explanation of the method of producing a polyether according to claims 22 to 25.
• GPC Gel permeation chromatography
• HLC-8020 gel permeation chromatograph product of Tosoh Corporation
• TSKgel GMH XL -L columns product of Tosoh Corporation
• the sample was submitted to measurement as the 2 weight% chloroform solution.
• the calibration curve was constructed using standard polystyrenes of known number-average molecular weight and weight-average molecular weight. The number-average molecular weight and the weight-average molecular weight were then determined in terms of the molecular weights of the standard polystyrenes.
• the polydispersity was calculated from the number-average molecular weight and the weight-average molecular weight.
• 13 C-nuclear magnetic resonance ( 13 C-NMR) analysis The measurements were carried out using a JNM-EX400 Fourier-transform nuclear magnetic resonance instrument from JEOL Ltd. The sample was dissolved in deuterochloroform or deuteromethanol and was measured with the addition of tris(acetylacetonato)chromium(III) as relaxation reagent.
• Liquid poly(methyl glycidyl ether)s having different average degrees of polymerization were prepared by carrying out polymerization and so forth under the same conditions as in Example 1, with the following exceptions: the amount of ethylene glycol monoallyl ether charged was changed from that in Example 1 and potassium t-butoxide was used in place of potassium hydroxide.
• Example 2 Example 3
• Example 4 Example 5 ethylene glycol monoallyl ether 1.86 g 18.2 mmol 0.93 g 9.1 mmol 0.46 g 4.5 mmol 0. 46 g 4.5 mmol polymerization catalyst t-BuOK 0.1 g 0.9 mmol t-BuOK 0.1 g 0.9 mmol t-BuOK 0.1 g 0.9 mmol t-BuOK 0.1 g 0.9 mmol t-BuOK 0.1 g 0.9 mmol yield 21.4 g 20.8 g 20.5 g 20.5 G % yield 98% 99.5% 100% 100% number-average molecular weight 1638 2678 4214 4139 polydispersity 1.063 1.053 1.078 1.082 average degree of polymerization (measured value) 12.3 25 48 46 degree of polymerization (calculated value) 12.5 25 50 50 50
• a liquid residue was obtained by carrying out polymerization and so forth using the same conditions as in Example 6, with the exception that 1.93 g (18.9 mmol) of ethylene glycol monoallyl ether was used in place of the 2.20 g (18.9 mmol) of ethylene glycol monobutyl ether used in Example 6. GPC analysis of this liquid residue gave a number-average molecular weight in terms of a standard polystyrene, of 1,635 and a polydispersity of 1.061.
• a commercially available poly(ethylene oxide) having an average degree of polymerization of 25 and capped at one terminal by the allyl group and at the other terminal by the carbinol group (BL-25T, trade name, from Nikko Chemicals Co., Ltd.) was a solid.
• the polyether of the present invention with general formula (1) and the polyether of the present invention with general formula (4) are useful as intermediates in the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction, as intermediates for the production of block copolymers, as reactive surfactants for emulsion polymerization, as monomers for copolymerization with other vinyl monomers, as a component of crosslinkable compositions, as a resin modifier, and so forth. They exhibit an excellent performance as an emulsifying agent for various oils and solvents.
• emulsifying agents and/or dispersants for various mineral oils, various plant oils, aliphatic hydrocarbon-type solvents, alicyclic hydrocarbon-type solvents, aromatic solvents, and various synthetic resins (e.g., various silicones, modified silicones, polyolefins, polyesters, and diene-type polymers such as polybutadiene); they are also useful as emulsifying agents and solubilizers for essential oils and fragrances.
• synthetic resins e.g., various silicones, modified silicones, polyolefins, polyesters, and diene-type polymers such as polybutadiene
• the polyether with general formula (1) or (4) in which R or R 2 is double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (C-O-C) therein and Y is hydrogen atom is useful as an intermediate for the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction, as a reactive surfactant for emulsion polymerization, and as a monomer for copolymerization with other vinyl monomers.
• the polyether with general formula (1) or (4) in which R or R 2 is double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (CO-C) therein and Y is a terminal double bond-free monovalent hydrocarbyl group having 2 to 20 carbon atoms or a terminal double bond-free acyl group having 2 to 20 carbon atoms is useful as monomer for copolymerization with other vinyl monomers and as an intermediate for the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• the polyether with general formula (1) or (4) in which R or R 2 is a terminal double bond-free monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (CO-C) therein and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms is useful as monomer for copolymerization with other vinyl monomers and as an intermediate for the production of polyether-modified organopolysiloxanes using the hydrosilylation reaction.
• the polyether with general formula (1) or (4) in which R or R 2 is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a group comprising said monovalent hydrocarbyl group having an ether linkage (CO-C) therein and Y is a double bond-terminated monovalent hydrocarbyl group having 2 to 20 carbon atoms or a double bond-terminated acyl group having 2 to 20 carbon atoms is useful as an intermediate for the production of block copolymers with diorganopolysiloxanes and as monomer for copolymerization with other vinyl monomers.
• the method of producing a polyether of the present invention are useful for the production, at high purities and high productivities, of poly(glycidyl ether)s and glycidyl ether ⁇ alkylene oxide copolymers that have a terminal double bond at one terminal and the hydroxyl group at the other terminal and that have a molecular weight distribution (polydispersity) determined versus a polystyrene standard of 1.25 to 1.00, poly(glycidyl ether)s and glycidyl ether ⁇ alkylene oxide copolymers that have a terminal double bond at one terminal and an aliphatically unsaturated bond-free group at the other terminal and that have a molecular weight distribution (polydispersity) determined versus a polystyrene standard of 1.25 to 1.00, and poly(glycidyl ether)s and glycidyl ether ⁇ alkylene oxide copolymers that have a terminal double bond at both terminals and that have a mo

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